{"title":"High-Density Formation of Ir/MoOx Interface through Hybrid Clustering for Chemoselective Nitrostyrene Hydrogenation","authors":"Shun Hayashi*, and , Tetsuya Shishido, ","doi":"10.1021/acsorginorgau.3c00017","DOIUrl":null,"url":null,"abstract":"<p >To form high-density metal/oxide interfacial active sites, we developed a catalyst preparation method based on hybrid clustering. An iridium–molybdenum (Ir–Mo) hybrid clustering catalyst was prepared by using the hybrid cluster [(IrCp*)<sub>4</sub>Mo<sub>4</sub>O<sub>16</sub>] (Cp* = η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>) as the precursor. The Ir–Mo hybrid clustering catalyst selectively reduced the nitro group in the hydrogenation of 4-nitrostyrene, whereas the coimpregnated Ir–Mo catalyst reduced both the nitro and vinyl groups nonselectively. The hybrid clustering catalyst also exhibited high selectivity, even at a high Ir loading (5 wt %), in contrast to Ir/MoO<sub>3</sub>, which exhibited high selectivity only at low Ir loadings (<0.3 wt %). In situ X-ray absorption spectroscopy analysis revealed that oxygen vacancies were formed at the Ir/MoO<sub><i>x</i></sub> interface in the presence of H<sub>2</sub>. We concluded that a high-density Ir/MoO<sub><i>x</i></sub> interface contributes to the preferential adsorption of nitro groups on vacant sites, promoting the selective hydrogenation of nitro groups.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3000,"publicationDate":"2023-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.3c00017","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Organic & Inorganic Au","FirstCategoryId":"1085","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsorginorgau.3c00017","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
To form high-density metal/oxide interfacial active sites, we developed a catalyst preparation method based on hybrid clustering. An iridium–molybdenum (Ir–Mo) hybrid clustering catalyst was prepared by using the hybrid cluster [(IrCp*)4Mo4O16] (Cp* = η5-C5Me5) as the precursor. The Ir–Mo hybrid clustering catalyst selectively reduced the nitro group in the hydrogenation of 4-nitrostyrene, whereas the coimpregnated Ir–Mo catalyst reduced both the nitro and vinyl groups nonselectively. The hybrid clustering catalyst also exhibited high selectivity, even at a high Ir loading (5 wt %), in contrast to Ir/MoO3, which exhibited high selectivity only at low Ir loadings (<0.3 wt %). In situ X-ray absorption spectroscopy analysis revealed that oxygen vacancies were formed at the Ir/MoOx interface in the presence of H2. We concluded that a high-density Ir/MoOx interface contributes to the preferential adsorption of nitro groups on vacant sites, promoting the selective hydrogenation of nitro groups.
期刊介绍:
ACS Organic & Inorganic Au is an open access journal that publishes original experimental and theoretical/computational studies on organic organometallic inorganic crystal growth and engineering and organic process chemistry. Short letters comprehensive articles reviews and perspectives are welcome on topics that include:Organic chemistry Organometallic chemistry Inorganic Chemistry and Organic Process Chemistry.